Cyclic diphosphono-carboxylic amides



United States Patent 0 3,381,062 CYCLIC DIPHOSPHONO-CARBOXYLIC AMIDESSheik Abdul-Caller Zahir, Great Shelford, Cambridge, England, assignorto Ciba Limited, Basel, Switzerland, a company of Switzerland NoDrawing. ()riginal application Apr. 27, 1964, Ser. No. 362,998. Dividedand this application May 11, 1967, Ser. No. 649,395 Claims priority,application Great Britain, May 3, 1963,

3/63 2 Claims. (Cl. 260927) This application is a division of SN.362,998, filed Apr. 27, 1964, now abandoned.

This invention relates to substituted phosphono-amides, to processes fortheir production, to compositions containing such compounds, and to theuse of such compositions to impart flame-resistance to cellulose andcellulosecontaining materials.

Numerous methods for treating cellulosic materials to impartflame-resistance thereto have been suggested. For example, mixtures ofboric acid or ammonium dihydrogen orthophosphate with borax have beenused to treat textiles, but the treatment must be repeated after eachwash. Methods of preparing wash-proof finishes include precipitation ofmetal oxides within or on the fibre, e.g. successive precipitation offerric oxide and a mixture of tungstic acid and stannic oxide orsuccessive precipitation of antimony trioxide and titanium dioxide.These are multi-bath processes involving the use of strongly acidicsolutions and are therefore inconvenient. Moreover, because there is asurface deposit on the textile of white metal oxide difficulties areencountered in subsequent dyeing processes.

A known single-bath process involving a metal oxide entails padding adispersion of a chlorinated hydrocarbon and finaly divided antimonyoxide on to the fabric and heating to render the finish wash-proof. Theactive agent in this case is antimony oxychloride which is formed by theinteraction of the oxide with the hydrogen chloride liberated from thechlorinated hydrocarbon when fiame temperatures are approached. Thehandle of the finished fabric is deleteriously affected and this isespecially so with fine, closely-Woven fabrics.

Esterification of cellulosic materials with, for instance, diammoniumhydrogen orthophosphate has also been used to impart flame resistance.It has the disadvantage that the treated material is susceptible toion-exchange in hard water or soap solutions, the inactive calcium orsodium salt being formed. The flame resistance must then be regeneratedby steppin the material in ammonium chloride solution.

Two more recent wash-fast flame-proofing finishes involve:

(1) Treatment of the cellulosic material with tetrakis(hydroxymethyl)phosphonium chloride in conjunction with an aminoplast.If all the components are used in the same bath the amount ofphosphonium salt and aminoplast which has to be absorbed in order toconfer adequate flame resistance is undesirably high, causing anincrease in weight of the treated fabric of 2025%. This massive additioncan modify the handle of the fabric and, moreover, many fabrics need tobe specially pretreated to render them sufficiently absorbent to take upsuch a large amount of proofing agent. A means of circumventing thisdifficulty is disclosed in British specification No. 884,785 and entailsthe use of a two-stage process in which the fabric is first treated withthe aminoplast and then with tetrakis (hydroxymethyl phosphoniumchloride.

(2) Treatment with a mixture of tetrakis (hydroxymeth- The treating bathis prepared immediately before use by mixing aqueous solutions of thetwo materials. It is unstable and must be kept cool. This process isalso twostage, because the fabric must be softened as an aftertreatment.Further, tris('aziridin-l-yDphosphine oxide is very toxic and excessmust be carefully washed from the fibre after the process is completed.Moreover, process workers must be protected.

The present invention provides a new class of substitutedphosphono-amides which can be used in conjunction with aminoplasts toconfer flame-resistance on cellulosic materials by a process whichavoids some or all of the disadvantages of known processes.

The new substituted phosphono-amides are those of the general Formula I:

pronnnr znoonrromoa where R represents hydrogen, allyl or alkyl of up tosix carbon atoms; n is either 1, when X represents hydrogen, methyl or a-CH CONHCH OR group, or zero, when X represents a CH CONHCH OR group;and R and R either each represent the same or different alkyl, alkenyl,cycloalkyl, cycloalkenyl, alkoxyalkyl, 'alkoxyalkenyl, aryl, alkoxyaryl,or alkylene residues, which may be substituted by one or more chlorineand/ or bromine atoms, the terminal valency of any such alkylene residuebeing linked to a group of Formula II:

P.(CH:)n.(|3H.CONHCHz0R O X II the free valency of which, if only one ofR and R is alkylene is linked to a further monovalent R or R residue, orR and R together represent a polymethylene chain containing from two tosix carbon atoms which may be linked to a second polymethylene chaincontaining two to six carbon atoms, via a spiro carbon, whichpolymethylene chains may be substituted by one or more chlorine and/ orbromine atoms and/ or methyl groups, the terminal valencies of thesecond polymethylene chain, if such be present, being linked to a groupof Formula II.

Preferred compounds of Formula I are those wherein R and R eitherrepresent identical alkyl groups, particularly those containing up tofour carbon atoms, or identical alkenyl or alkylene groups, particularlythose containing from two to four carbon atoms; or together represent apolymethylene group containing from two to six carbon atoms. Alsopreferred are those compounds wherein R and R together represent apolymethylene chain containing from two to three carbon atoms linked toa second such polymethylene chain via a spiro-carbon. Further preferredare those compounds of Formula I wherein each of R and R contains up tofour chlorine and/ or bromine atoms.

Specific examples of preferred compounds areN-hydroxymethyl-3-(diethylphosphono) propionamide,

N-hydroxymethyl-3-( diallylphosphono)propionamide,

N-methoxymethyl-3-(bis(2,3-dichloropropyl)phosphono) propionamide,

N-hydroxymethyl-3- diethylphosphono) -2-methylpropionamide,

Patented Apr. 30, 1968 3 4N-hydroxymethyl-3-(2,2-dimethyltrimethylenephostions Nos. 2,754,319 and2,754,320. They can be made by phono)propionamide, reacting a mono ordi-phosphite ester or Formula VIII: N-hydroXymethyl-3-(1-methyltrimethylenephosphono) O propionarnide, N-hydroxymethyl-S-(bis(bromotrichloropropyl)phos- 5 phono propionamide, R 0 H VIII y y y y p p)P p wherein R and R are as hereinbefore defined except that referencesto the on and those of the formulae: 0 gr p C2H5O 0 (.(CH )n.CHCONHCHzORP.0HzCHCONHCHzOH m 021150 CHCONHCHOH should be understood as referencesto the group and -O O CzH5O o \l l H P.(IJHCONHCHZOH IV 02H) CHCONHCHOHwith acrylamide, methacrylamide, itaconamide, fumar-- and those of theformulae: amide or maleamide.

li/ \ii HO Cumnooomomr /o\ P.0H2CH2CONHCH3OH O-GHZ CH2O VI i)O-CH2CH:-O\I) H0 CHgNHCOCHzCH E eoHzomooNnofliorr OGHZCHZO VII wherein RR n and X are as hereinbefore defined except that reference to the groupare to be understood as references to the group in neutral or alkalinesolution with formaldehyde or a substance liberating formaldehyde underthe reaction conditions.

It is preferred to add the compound of Formula VII to an aqueoussolution of formaldehyde, the pH of the reaction mixture beingmaintained at or above 7.0 by the addition of an alkaline-reactingsubstance, suitably sodium hydroxide, and to maintain the temperature ofthe reaction mixture between C. and C. After the reaction is completed,the solution may be cooled and filtered. The product may be incorporatedin the flameproofing compositions hereinafter described as the aqueoussolution so obtained.

Another preferred method comprises heating a compound of Formula VIIwith paraformaldehyde in the presence of an alkaline-reacting substance,suitably potassium carbonate or sodium carbonate. Temperatures betweenabout C. and about C. may be employed, if 'a solvent, such'as methanolis added, reaction may be effected at lower temperatures, e.g. about 50C. Compounds of the general Formula VII have been described by A. N.Pudovick and D. Kh. Yarmukhametova (Bull. Acad. Sci. U.S.S.R., Div.Chem. Sci,

1952, 657-660) and in United States Patent specifica- It is usual toconduct the reaction in the presence of a non-acidic condensationcatalyst, preferably an alkaline catalyst. The latter may be an alkalimetal, an alkaline metal amide, an alkali metal hydride, a secondary ortertiary amine, an alkali metal salt of the phosphite diesters, aquaternary ammonium hydroxide or basic ionexchange resin and,especially, a solution or slurry of an alkali metal alkoxide in thecorresponding alcohol. The reaction, after an induction period, becomesvigorously exothermic and the mixture may be cooled as necessary. Avolatile inert solvent, particularly a high-boiling liquid, may be addedto moderate the reaction. Addition of a solvent is desirable but notessential, when the unsaturated amide is a solid under the reactionconditions.

According to a further feature of the invention a process for theproduction of compounds of the general Formula I wherein R=H comprisesreacting one to two molar proportions of anN-hydroxymethyl-a,,3-unsaturated amide of the Formula IX:

X IX

wherein n is either 1, when X represents hydrogen, methyl or a CH CONHCH group, or zero, when X represents a CHCO.NH OH group, with one molarproportion of a phosphite or diphosphite of Formula VIII.

According to a still further feature of the invention, compounds of thegeneral Formula I wherein R denotes an alkyl group containing from oneto six carbon atoms, are produced by reacting a compound of Formula I inwhich R is hydrogen with an aliphatic monohydric alcohol containing fromone to six carbon atoms, in the presence of an acid.

According to another feature of the invention, compounds of the generalFormula I wherein R denotes an allyl group are produced by reacting acompound of Formula I in which R is hydrogen with allyl alcohol in thepresence of an acid.

According to further features of the invention compounds of the generalFormula I wherein R denotes an alkyl group containing from one to sixcarbon atoms or an allyl group are prepared by reacting a compound ofFormula VIII with one to two molar proportions of an N-alkoxymethylor Nallyloxymethyl-a,fi-unsaturated amide of the Formula X:

(CHFMQCONHCHQOR wherein n, X and R are as hereinbefore defined.

Compounds of the general Formula IX have been described in Britishpatent specification No. 482,897, and by Kamogawa, Muraso and Sakiys(Textile Res. 1., 1960, 30, 774-81). Compounds of the general Formula Xhave been described by Muller, Dinges and Graulich (Makromol. Chem.,1962, 57, 27).

The invention includes within its scope compositions of utility inimparting flame-resistance to cellulosic materials, which contain atleast one compound of the general Formula I having one -CONHCH OR groupand an aminoplast, or at least one compound of the general Formula Ihaving two -CONHCH OR groups and, optionally, an aminoplast. Preferably,such compositions also contain a latent acid catalyst to acceleratecuring of the aminoplast and cross-linking of the compound of thegeneral Formula I having two CONHSH OR groups. The latent acid catalystwhich may be used are wellknown in the process of curing aminoplasta oncellulcsic materials, and include for example, ammonium chloride,ammonium dihydrogen orthophosphate, magnesium chloride, zinc nitrate,etc. The aminoplast employed may be a condensation product offormaldehyde with urea or a derivative thereof such as ethyleneurea, or,preferably, with melamine or a derivative, such as an ether, of the saidmelamine-formaldehyde condensation product. A process for renderingcellulose-contaning materials flameresistant by treatment with such acomposition followed by heating the treated material to cure the saidaminoplast, and/or to effect cross-linking of the compound of generalFormula I containing two CONHCH OR grups is within the scope of theinvention.

Compounds of general Formula I containing chlorine and/or bromine atomsmay be prepared by using halogen-containing starting materials in theaforesaid processes or by halogenation of the intermediates or finalproducts. Particularly preferred halogen-containing compounds are thoseobtained by reaction of 3-(diallyl-phosphono)propionamide with apolyhalogenated methane, espcially bromotrichloromethane, in thepresence of a free-radical catalyst such as benzoyl peroxide, followedby hydroxymethylation.

Compounds of Formula I in which one or more of R, R and R are allylgroups may be polymerised in the presence of a free-radical catalyst togive polymers which may be used for flame-proofing cellulosic materialsin the same way as the compounds of Formula I themselves. Such products,compositions thereof with amino plasts, and the use of such products andcompositions as flame-proofing agents, constitute further features ofthe invention.

The following examples illustrate the invention.

Example I.-Preparation of N-hydroxymethyl-3-(diethylphosphono)propionamide Freshly-prepared ethanolic sodiumethoxide solution (2.90 M, 70 ml.) was added slowly to a solution ofacrylamide (568 g., 8 moles) in freshly-distilled diethyl phosphite(2208 g., 16 moles). A vigorous exothermic reaction occurred after abouthalf of the sodium ethoxide solution had been added; the temperature ofthe reaction mixture was maintained at 80-90 C. by further cautiousaddition of the catalyst until the exothermic reaction had subsided. Theproduct was isolated by seeding the cooled solution and filtering offthe precipitated crystals. These were washed with benzene and dried. Theyield of 3-(diethylphosphono)propionamide was 1277 g. and a further 400g. was isolated by evaporating the filtrate in vacuo to dryness. Theproduct had a melting-point of 73.5-

6 74.5 C. Elementary analysis gave the following results: P: 15.3%;N=6.7%; C H NO P requires P: 14.85%; N=6.7%.

The propionamide (1440 g.) was then added gradually to formalin (36.5%,564 g.) at C., the pH of the mixture being maintained at 7.5-8.0 byadding approximately 5 ml. of 40% caustic soda solution. After themixture had been stirred for 2 hours it was allowed to cool to roomtemperature and filtered. Approximately 2000 g. of an 82.0% solution ofN-hydroxymethyl-3- (diethylphosphono)propionarnide was obtained.

A sample of the solution was evaporated to dryness in vacuo. Elementaryanalysis of the residue gave the following results: P=12.3%; N:5.0%; C HNO P requires P=12.95%; N=5.9%.

The infra-red spectrum of the product indicated it to be the requiredN-hydroxymethyl compound by the presence of the characteristic amide-IIband at 1550 cm. and a broad band at about 3350 cm? due to the hydroxylgroup and NH-stretching on the secondary amide.

Example II.Preparation of N-hydroxymethyl-3-(dimethylphosphono)propionamide Methanolic sodium methoxide solution(3.04 M, 115 ml.), was added to acrylamide (284 g., 4 moles) in dimethylphosphite (440 g., 4 moles) and dioxane (400 ml.). A vigorous exothermicreaction ensued when about 90 ml. of the sodium rnethoxide solution hadbeen added, and the temperature of the reaction mixture was maintainedat 80-90 C. by adding further quantities of the catalyst. The mixturewas cooled to room temperature and the dioxane distilled in vacuo toleave 3-(dimethylphosphono)propionamide as a white solid; yield, 600 g.

This product (271.5 g., 1.5 moles) was added in portions to 36.5formalin solution (123 g., 1.5 moles) at -60 C. The pH of the mixturewas maintained at 8.0 by the addition of 40% caustic soda solution,about 1 ml. being required. The reaction mixture was stirred for 1 hourat C., cooled and filtered to give a solution of the desired product.

Example III.-Preparation of N-(hydroxymethyl)-3-(diallylphosphono)propionamide Proceeding as in Example I, methanolicsodium methoxide solution (4.35 M, 35 ml.) was added to acrylamide (72g., 1 mole) in diallyl phosphite (162 g., 1 mole) and dioxane (250 ml.),a vigorous exothermic reaction ensuing when 32 ml. of the sodiummethoxide solution had been added. The yield of the intermediate was213.2 g.

This compound (119 g.) was similarly hydroxymethylated with 36.5formalin solution (41 g.) at 55-60 C. and a solution of the desiredproduct obtained, as described in Example 1.

Example IV .-Preparation ofN-hydroxymethyl-3-(diisopropylphosphono)propionamide A slurry of sodiumisopropoxide in isopropanol (equivalent to 4% w./w. of sodium) was addedslowly to acrylamide (142 g.) dissolved in di-isopropyl phosphite (332g., 2 moles) and dioxane (300 ml.). An exothermic reaction set in aftersome g. of the catalyst had been added, and the total amount of catalystadded before the exothermic reaction had ceased was g. The intermediatewas induced to crystallise (in a yield of 456 g.) by adding a smallpiece of solid carbon dioxide to the cooled solution.

This intermediate (237 g.) was treated with 36.5% formalin solution (82g.) at 5560 C., about 0.2 ml. of 40% caustic soda solution being added.The reaction mixture was stirred for 2 hours at 60 C., cooled andfiltered to give a solution of the desired product.

Example V.-Preparation of N-hydroxyrnethyl-3-(bis-(2,3-dichloropropyl)phosphono)propionamide A 3.6 M methanolic solutionof sodium methoxide (8 ml.) was added slowly to acrylamide (7.1 g.) inbis- 7 (2,3-dichloropropyl)phosphite (30.4 g.) and dioxane (30 ml.).After evaporation of the solvent in vacuo the residue was added to 36.5%formalin solution (8.2 ml.); the reaction mixture was maintained at pH 8and at 50 C. For ease of stirring the mixture was diluted with waterduring the reaction. A solution of the desired product was obtained.

Example VI.-Preparation of N-hydroxymethyl-3-l-methyltrimethylenephosphono) propionamide A mixture of acrylamide(59.3 g.) and 112 g. of the cyclic phosphite ester of butane-1,3-diol(prepared by transesterifying the diol with diethyl phosphite) in 100ml. of dioxane was treated with methanolic sodium methoxide solution(5.6 M; 20 ml.), as described in Example I. A vigorous exothermicreaction ensued when about 14 ml. of the catalyst had been added.

The residue obtained by evaporation in vacuo of the solvent was addedgradually to 36.5% formalin (67.5 g.). The mixture was maintained at 60C. and at pH 8 during the addition, then stirred for 2 hours at 50 C.,cooled and filtered. A solution of the desired product was obtained.

Example VH.Preparation of N-hydroxymethyl-3-dicyclohexylphosphono)propionamide Phosphorus trichloride (27.5 g., 0.2 mole) in dioxan (40ml.) was added slowly to cyclohexanol (60 g., 0.5 mole) with vigorousstirring, the hydrogen chloride formed being removed in a stream ofnitrogen. The mixture was refluxed for 1% hours, and then heated at 100C. under a water pump vacuum and finally at 0.5 mm. pressure. Theresidue weighed 41.5 g. (84.5% yield).

A mixture of the dicyclohexyl phosphite so obtained (64.5 g., 0.26 mole)and acrylamide (18.6 g., 0.26 mole) was treated until alkaline with asaturated solution in cyclohexanol of sodium cyclohexoxide. A very smallquantity of ethanolic sodium ethoxide was then added, further additionsbeing made when the exothermic reaction had subsided. The solution wasneutralized with glacial acetic acid, and volatile materials distilledoff by heating the mixture at 100 C. under about 12 mm. pressure.

The residue, the infra-red spectrum of which indicated it to be therequired 3-(dicyclohexylphosphono)propionamide was stirred withparaforrnaldehyde (7.86 g., 0.26 mole) and anhydrous potassium carbonate(0.2 g.) at 120 C. for 2 /2 hours.

Example VIII.Preparation of N-hydroxymethyl-3-(2,2-dimethyltrimethylenephosphono propion amide Neopentyl glycol (312 g., 3moles), diethyl phosphite (414 g., 3 moles) and 5.5 N-methanolic sodiummethoxide solution (6 ml.) were heated together for 6 hours, the ethanolevolved being separated. On fractional distillation of the residue therewas obtained 355 g. of the cyclic phosphite of neopentyl glycol, havinga B.P. of 132 C. at 2 mm. and an M.P. of about 53 C.

To 15 g. (0.1 mole) of the cyclic phosphite and 7.1 g. (0.1 mole) ofacrylamide in 10 ml. of dimethylformamide was added dropwise .5N-methanolic sodium methoxide solution. After the exothermic reactionhad subsided, the mixture was cooled and allowed to stand overnight. Thedesired intermediate separated as a fine white powder, M.P. 1905 C.

The intermediate (11.05 g., 0.05 mole), parafonmaldehyde (1.5 g., 0.05mole) and methanol (25 ml.) were heated at 50 C. for 1 hour, the mixturebeing kept at pH 8.0 by addition of a few drops by concentratedmethanolic sodium methoxide solution. The hydroxymethyl derivativeremained as a clear, resinous liquid on evaporation of the solvent.

Example IX.--Prepa-ration of the bis(N-hydroxymethylpropionamide)derivative of pentaerythritol diphosphite (A) Phosphorus trichloride(530 g., 4 moles) was added slowly to pentaerythritol (136 g., 1 mole),and the mixture heated slowly to 63 C. The clear solution so obtainedwas refluxed for 1% hours, and unreacted phosphorus trichloride was thendistilled off. The residue, which solidified on cooling, was dissolvedin chloroform (200 ml.), and a mixture of ethanol (92 g.) in chloroform(100 ml.) was added in portions over about 30 minutes, the rate ofaddition being adjusted so as to moderate the rate of refluxing. Themixture was filtered and the chloroform distilled off. A pale yellow,clear, resinous liquid remained, the infra-red spectrum of whichindicated the presence of PH bonds.

Acrylamide (108.7 g., 0.75 mole) was added to a solution of thismaterial (172.2 g., 0.75 mole) in dimethylforamide (300 ml.).Concentrated methanolic sodium methoxide solution (30 ml.) was thenadded dropwise. When the exothermic reaction had subsided, the solventswere distilled ed. A glassy solid (280 g.) remained.

This solid was melted and added portionwise to 36.5% formalin (123.5g.), the mixture being maintained at pH 8.0 by addition of aqueous 40%sodium hydroxide and at 50 C. for 2 hours. The mixture was cooled andfiltered, 437.5 g. of a clear resin being obtained.

(B) The desired product was also prepared in the following manner.

Pentaerythritol .(68 g., 0.5 mole) was transesterified with diethylphosphite (276 g., 2 moles) in the presence of concentrated ethanolicsodium ethoxide solution (5 ml.), g. of ethanol being collected over 2/2 hours. Unchanged diethyl phosphite was then distilled off. Theviscous, colourless residue (105.2 g.) set to :a glassy solid oncooling.

The intermediate was reacted with acrylamide (64.5 g.) in dimethylformamide (200 m1.) asdescribed above, 40 m1. of 4.4 M-methanolic sodiummethoxide solution being added. After distilling off the solvents, 185g. of a resinous material remained. This was then reacted with 36.5%formalin (27.2 g.) as previously described.

Example X.--Preparation of N-hydroxymethyl-3-(nbutyl ethylphosphono)propionamide A mixture of diethyl phosphite .(276 g., 2 moles), nbutanol(148 g., 2 moles) and concentrated ethanolic sodium ethoxide solution (5ml.) was heated, the ethanol evolved being separated. When ethanol wasno longer evolved (i.e., after 3 hours), the residue was fractionated.The fraction boiling at 105 C./l7 mm. (n 1.4164) was shown by gas liquidchromatography to be n-butyl ethyl phosphite.

A concentrated solution (4 ml.) of sodium ethoxide-and sodium n-butoxide(made by dissolving sodium in an equimolar mixture of ethanol andbutanol) was added dropwise to n-butyl ethyl phosphite (32.5 g., 0.196mole) and acrylamide (13.9 g., 0.196 mole). After the vigorous reactionhad been completed, volatile materials were distilled 011', and theviscous residue induced to crystallise by cooling to 0 C. The crudeintermediate melted at about 18 C.

This intermediate (23.9 g., 0.1 mole), paraformaldehyde (3.1 g.) andanhydrous potassium carbonate (0.2 g.) were heated at C. for 2 hours toyield the desired product as a yellow, viscous resin.

Example XI.Preparation of the bis(N-hydroxymethylpropionamide)derivative of ethylene glycol diphosphite Diethyl phosphite (82.8 g.,0.6 mole) ethylene glycol (37.2 g., 0.2 mole) and a small piece ofsodium were heated for 5 hours at -45 C. and 200 mm. pressure. Onfractional distillation of the mitxure, 37 g. of a product having B.P.118 C./0.2 mm. and n =1.4750 were obtained. Petrov et al. (Zhur.Obahobel Khim., 1963, 33 1485) report a B.P. of 1326 C./2.5 mm. and m1.4753.

This product (37 g., 0.171 mole) was dissolved in tetrahydrofuran (50ml.), and mixed with acrylamide (24.3 g., 0.342 mole) dissolved intetrahydrofuran (50 ml.). The mixture was treated with concentratedethanolic sodium ethoxide solution until an oxothermic reaction nolonger occurred, and was then neutralised with glacial acetic acid.After removal of volatile materials by heating the mixture at 100 C. atthe water pump, the product was hydroxymethylated by being stirred at120 C. for 2 /2 hours with paraformaldehyde (10.3 g., 0.342 mole) andanhydrous sodium carbonate (0.3 g.)

Example XII.-Preparation of N-hydroxymethyl-3-(diethylphosphono)-2-methylpropionamide 2.6 M-ethanolic sodium ethoxide solution (20 ml.)was added dropwise to methacrylamide (42.5 g., 0.5 mole) dissolved indiethyl phosphite (350 g., 2.53 moles), a vigorous exothermic reactionoccurring. Unchanged diethyl phosphite was then distilled 01f, and theresidue allowed to solidify on cooling.

The residue (22.3 g., 0.1 mole), paraformaldehyde (3.0 g.) and anhydrouspotassium carbonate .(0.1 g.) were stirred together at 120 C. for 2hours. The product was a yellow viscous liquid.

Example XI1I.-Preparation of N-hydroxymethyl-3-(bis (2-ethoxyethyl)phosphono) propionamide) Di(2-ethoxyethyl)phosphite was obtained in198.6 g. yield and having a B.P. of ll8121 C./ 1.4 mm. by heating2-ethoxyethanol (180.2 g., 2 moles), diethyl phosphite (138 g., 1 mole)and 2.5 ml. of concentrated ethanolic sodium ethoxide solution for 8hours, the liberated ethanol being separated.

5.5 M-methanolic sodium methoxide solution (0.8 ml.) was then addeddropwise to di(2-ethoxyethyl) phosphite (22.6 g., 0.1 mole) andacrylamide (7.1 g., 0.1 mole), a vigorous exothermic reaction ensuing.On cooling the mixture it set to a white solid having an M.P. of 41-44C.

The resultant phosphonopropionamide (14.85 g.) was then added to 36.5aqueous formaldehyde solution (4.5 g.), the mixture being heated at 50C. for 1 hour, and maintained at pH 8 by the addition of a few drops of40% aqueous sodium hydroxide solution.

Example X1V.Preparation of N-methoxymethyl-3- (diethylphosphono)propionamide 3-(diethylphosphono)propionamide (418 g., 2 moles),prepared as described in Example 1, paraformaldehyde (60 g., 2 moles)and anhydrous potassium carbonate (2 g.) were stirred together at 120 C.for 2 /2 hours.

To the cooled reaction product was added methanol (500 ml.), and the pHof the mixture was adjusted to 2.5-3 by adding ml. of methanolichydrogen chloride solution. The mixture was refluxed for 1 hours,cooled, neutralised with sodium carbonate, filtered, and excess methanoldistilled 01f. The residue was a light yellow viscous liquid having anitrogen content of 5.56% (theoretical value, 5.55)

Example XV.--Preparation of N,N-bis(hydroxymethyl)-3-(diethylphosphono)methylsuccinamide To a mixture of dimethyl itaconate(474 g., 3 moles) and diethyl phosphite (414 g., 3 moles) was addeddropwise 5.5 M-methanolic sodium methoxide solution. A vigorousexothermic reaction ensued. The mixture was neutralised with glacialacetic acid, filtered, and the filtrate distilled. The yield of dimethyl3-(diethylphosphono)- methylsuccinate, having B.P. 1726 C./2 mm. and n1.4448, was 713.5 g., i.e., 80%.

Ammonia gas was passed into a mixture of the ester (687.3 g.) andmethanol (3 litres) for about six hours, i.e. until the mixture wassaturated. The mixture was allowed to stand at room temperature for oneweek, and was then concentrated. The succinamide crystallised out in ayield of 402.7 g. and was filtered oil. The succinamide had an M.P. of173-8 C. Elementary analysis gave the following results:

Found C=39.80; H=7.22; N=.10.42; P=11.68%. C H N O P requires C=40.60;H=7.19; N=10.52; P=1l.63%.

The succinamide (26.6 g.) was dissolved in methanol (100 ml.), andparaformaldehyde (6.0 g.) was added, followed by a few drops ofmethanolic sodium methoxide solution to adjust the pH of the mixture to9.0. The mixture was then stirred at 50 C. for 3 hours.

Example XVI.-Preparation of N-allyloxyrnethyl 3(diethylphosphono)propionamide Acrylamide (71 g.), paraformaldehyde (33g.) and allyl alcohol (68 ml.) were heated at 50 C. for 2 hours, themixture being maintained at pH 9.0 by addition of a few drops of 40%aqueous sodium hydroxide solution. A further 250 ml. of allyl acohol,and 1 g. of hydroquinone were added, the solution was acidified withmethanolic hydrogen chloride solution to a pH of approximately 2.5, andthen heated at 90 C. for 6 hours. After neutralisation of the mixturewith sodium carbonate, followed by filtration, the filtrate wassubjected to flash-distillation. N-(allyloxymethyl)arylamide wasobtained in 80% yield, and having a B.P. of 103-l04 C./0.2 mm. and n=1.4820.

A concentrated ethanolic solution of sodium ethoxide was added dropwiseto a mixture of N-(allyloxymethyl) acrylamide (14.1 g.) and diethylphosphite (138 g.). After the exothermic reaction had ceased, thesolution was neutralised with methanolic hydrogen chloride solution,filtered, and unchanged diethyl phosphite distilled 0E. The residue (28g.), was a clear, colourless liquid, shown by infrared spectroscopy tobe the addition product of diethyl phosphite andN-(allyloxymethyl)acrylamide.

Example XVII. Polymerisation of N-hydroxmethyl- 3-(diallyphcsphono)propionamide To 16.45 g. of N-hydroxymethyl-3-(diallylphosphono)propionamide was added 0.3 g. of ammonium persulphate, and the solutionwas heated at 70 C. under nitrogen for 4 hours. A clear, viscous, liquidwas obtained.

Example XVIlI.-Preparation of N-hydroxymethyl-3-(bis(bromotrichloromethylpropyl) phosphono)propionamide To3-(diallylphosphono)propionamide, prepared as described in Example III,was added 200 g. of bromotrichloromethane and 2 g. of benzoyl peroxide.The mixture was heated at 65 C. for 3 hours in an atmosphere ofnitrogen.

Dioxan and unreacted bromotrichloromethane were then distilled 08 underreduced pressure, and the residue hydroxymethylated in ml. of methanolby reaction with 100 ml. of 36.5% aqueous formaldehyde solution at 70 C.for 2 hours, the mixture being kept at a pH of approximately 8 byaddition of 5 ml. of a 50% aqueous solution of sodium hydroxide. Onevaporation of volatile materials, the desired product was obtained as aredbrown residue.

Example XIX.Preparation of N,N'-bis(hydroxymethyl) -2-(diethylphosphono)succinamide Di n propyl 2 (diethylphosphono)succinate,having B.P. 134-6 C./0.5 mm. and n =l.4398, was prepared fromdi-n-propyl maleate and diethyl phosphite as in Example XV, aconcentrated ethanolic solution of sodium ethoxide being used ascatalyst. W

The ester was then reacted with methanolic ammonia as in Example XV. Theresultant succinamide, which had an M.P. of 187-9 C. was thenhydroxymethylated in methanol with paraformaldehyde in the presence ofmethanolic sodium methoxide solution as described in Example XV.

1 1 Example XX Mixtures having the following compositions were prepared,the figures representing the Weight in grams of the substances added toone litre of water.

5 method (SNV-95 821 ASSESSMENT OF SAMPLES Mixture No.

Appearance:

Before washing. Normal Normal Normal Normal Normal Normal.

After washingo do do do do- Do. Handle:

Before washing. Soft Harsh." Full- Full- Full- Full.

After washing do do do do do Do. Flammability index:

Before washing 2 4-5 2 3 1 3.

After washing 2 3-4 3. 1 3.

Mixture No.

83% WW aqueous solution ofN-hydroxymethyl-3-(diethylphosphono)proplonamide 200 200 200 200 200Product A 150 Product B.-. Product 0... Anhydrous so on Magnesiumchloride hexahydrate Bleached cotton fabric was padded with eachsolution 35 to' give a weight increase of 80-85%, dried at 80 C.,

and cured for 4.5 minutes at l55-l60 C. The fabric sample from bath No.l was also rinsed in cold soft water.

ASSESSMENT 'OF SAMPLES Example XXII N (hydroxymethyl 3(diethylphosphono) propionarnide was incorporated ('as an aqueoussolution) into decorative paper-melamine formaldehyde laminates.Flame-proofing properties were evaluated by the Surface Spread of FrameTest (British Standard Specification No. 476, Part 1, 1953). The resinemployed vwas used as a aqueous solution and prepared by the reaction'ofmelamine (1 part by weight) with formaldehyde (2.45 parts by weight, asan aqueous solution); it was cured at 145 C.

Mixture No.

A arance Normal. NormaL Normal. Normal. Normal- Normal. Hgr il ile SoftSoft Soft.--" Soft Soft Soft. Flammability index 5 3 4 4 2 3 Theflammability index values were assigned according to the arbitraryscale: 5=non-infiammable t0 Method of Impregnation Amount offlame-proofing Result 1=easily inflammable. agent added Paperspretreated with the 20 i.e. 2.0 P on wei ht Class 1. Example XXI 50solution, dreid, treated with Zf paper. g the resin, and cured. Mixtureshavmg the following compositions were pret P on ieight of Class '0 gecora ive paper ayer. pared, the figlfres agam represe ntmg the WelDht mgram 38% on weight of decorative Class 1. of each material added to onelitre of water. paper layer and 53%, Le.

7% P, on overlay. Mixture N0. 5 5

Added to solution of resin be- 22 g. of solution to 78 g. of Class 2. 78 9 10 11 12 fore using. l i d 3 P (ml-e511] so s. Aqueous solution518137?!) ofxN-hy- Btsizilcdzgcid, 4% on main D th l-3- t as ono Igifiitiimlu. e y p p 400 400 400 400 400 400 Born; acid, 5 on resin DProduct A 1 sollds (adjusted to pH 7 bydaddition of caustic so a Product1?. Ammonium dihydrogen orthophosphate 2O 20 Magnesium chloridehexahydrate 20 Ammonium chloride 2 2 2 Product D was a aqueous solutionof a highly etherified polymethylolemamine.

Product E was an aqueous emulsion containing 50% of a copolymer derivedfrom vinylidene chloride and an alkyl acrylate.

Product F was a commercially-available nonionic wetting agent derivedfrom ethylene oxide.

Samples of a bleached cotton fabric and a bleached spun viscose materialwith raised woven effects were Both laminates prepared with boric acidhad poor sur- 5 faces and appeared to have undergone pre-curing.

Example XXIII A halogenated product, believed to consist essentially of7 N hydroxymethyl 3(bis(bromotrichloromethylpropyl)phosphono)propionamide, prepared asdescribed in Example XVIII, was similarly evaluated as a flame-proofin gagent. The resin employed was the melamine-formaldehyde resin used inExample XXII and was cured under padded to a weight increase of 80%(cotton) or 75 similar conditions.

Method of Impregnating Amount of flame- Result Mixture No proofing agentadded 13 14 15 16 Papers pretreated with aqueous 18% m decoratlve paper-Class 2.

solut1on and dried, then treated 26%u1overlay r- D0.N-hydroxymethyl-3-(diethylphosphono)propion- 300 with resin and cured.14% m decorative paper. Class 2. amide 20% overlayN-hydgoxyrnethyl-Ii-(dimethylpho hono)pro arm e e. 300 Added to resinsolution before cur- 18.8% (1.5% P) on resin- Class 1.N-hydmxymethyl-Zt-(bis(2-ehloroethyl)phosphonocuring. 37.5% (3% P) onresin. C1258 3. propionamide 300 u 62% P) Class N-hydroxymethy1-3-(l-rnethyltrimethylenephosphono)propionamide 300Product D 5 135 135 135 Exam l XXIV Annnonlurn chloride 5 5 5 5 i qfiannekitte was Padded Wlth an aqueous Z P Cotton fabric was padded witheach solution to a Contammg per of N'methoxymethyl'a'wle' weightincrease of 80%, dried at 80 C. and cured for g i gif i ga of i and 4.5minutes at 160 C. Part of the fabric was washed d g fi 3 e me $2 19 fivetimes accordingly to test C of SN V-95821. The ea e a or E 6flammability indices of the fabric, determined as in treated fabric metthe requirements of Bntlsh Standard EmmPleXX were. Specification No.3119 (1959). A

Example XXV 20 Mixture Cotton flannelette was padded with an aqueoussolution 13 14 15 15 containing, per litre, 300 g. ofN-hydroxymethyl-Ia-(di- Flammability Index:

Before washin 5 5 5 5 ethylphosphono) propronannde, 140 g. of Product D,After washmgiu H H 4 4x5 50 g. of a commerclally avallable polyethylenewax emulsion employed as a textile softening agent, and 5 g. of ammoniumchloride, to a weight increase of 80%. The treated 1s clalmeds' f f r 1material was dried at 80 C. and then heated for 5 minutes e compoun O 0mu Ii/ \ii HOCHzNIICOCHgCHaP /C\ P.CH:CH2CONHCH2OH O-CH2 CH2O at 155 C.Part of the material was submitted to the Washll HO CHzNHCO CHzCHz.P

Example XXVI Mixtures having the following compositions were prepared,the figures representing the Weight in grams of each material added toone litre of water.

2. The compound of formula:

References Cited UNITED STATES PATENTS 3,141,032 7/1964 Friedman 260927CHARLES B. PARKER, Primary Examiner.

A. H. SUTTO, Assistant Examiner.

1. THE COMPOUND OF FORMULA:
 2. THE COMPOUND OF FORMULA: